JP2013049599A - Production apparatus of fibrous carbon material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production apparatus capable of improving its production efficiency, when producing a carbon nanocoil or the like by using a fluid bed.SOLUTION: This apparatus includes: a cylindrical member 1 whose upper and lower ends are blocked; a reversely-conical fluid bed holding member 2 partitioning the cylindrical member into an upper space part A for forming the fluid bed and a lower space part B for supplying reaction gas by being arranged on a middle part in the cylindrical member, and having a takeout opening part 2a of a product formed on the center; a takeout cylinder member 3 for guiding a product on the holding member to a recovery means 4; an opening/closing means 5 for opening/closing the takeout opening part; a granular material supply means 6 for supplying a granular material into the upper space part of the cylindrical member; a reaction gas supply means 7 for supplying reaction gas into a circular space part C between the takeout cylinder member and the cylindrical member; a heating means 8 arranged on the outer periphery of the cylindrical member, and capable of heating the inside thereof; and a scraping means 9 arranged in the upper space part of the cylindrical member, and capable of scraping adhesives adhering onto the inner wall surface of the cylindrical member.

Description

  The present invention relates to an apparatus for producing a fibrous carbon material.

  Conventionally, a thermal CVD apparatus has been used as an apparatus for producing carbon nanotubes, but there is an apparatus using a fluidized bed as an apparatus for efficiently producing carbon nanotubes (for example, see Patent Document 1).

  In this manufacturing apparatus using a fluidized bed, a fluidized bed is disposed in a cylindrical tank, a gas for forming a fluidized bed is supplied from the bottom, and a carbon gas as a raw material is supplied. It is a thing. Of course, a heating means is provided around the tank, and the inside of the tank is heated to a predetermined temperature.

JP 2003-342840 A

  In the above-described manufacturing apparatus, the material that forms the fluidized bed is a material in which the carrier carrying the catalyst is bound with a binder, so that the raw material and the catalyst are sufficiently contacted to efficiently produce the carbon nanomaterial. Although it is a batch type, by-products such as soot and tar are generated during the thermal CVD, and this by-product adheres and grows on the inner wall surface of the tank, resulting in inconvenience in taking out the product, and extending the length. However, there is a problem that the production efficiency is lowered.

  Therefore, the present invention has an object to provide an apparatus for producing a fibrous carbon material capable of improving the production efficiency when producing a fibrous carbon material such as carbon nanocoil and carbon nanotube using a fluidized bed. And

In order to solve the above-mentioned problems, the apparatus for producing a fibrous carbon material according to claim 1 of the present invention fluidizes and heats a granular material in which a catalyst is supported on particles using a reaction gas containing carbon. By this, an apparatus for producing fibrous carbon material by growing fibrous carbon on a granular material,
A cylindrical member that is arranged in the vertical direction and whose upper and lower ends are closed, and is divided into an upper space part for forming a fluidized bed and a lower space part for supplying a reactive gas, which are arranged in an intermediate part in the cylindrical member. And an inverted conical fluidized bed holding member in which an opening for extraction of the fibrous carbon material is formed in the center and a plurality of gas introduction holes are formed near the outer periphery of the extraction opening, and in the lower space portion A tubular member for taking out carbon fiber material, the upper end opening of which is connected to the extraction opening and the lower end opening of which can be connected to the collecting means, and the extraction opening can be opened and closed freely. Reactive opening / closing means, granular material supply means for supplying granular material to the upper space of the cylindrical member, and reactive gas for supplying reactive gas into the annular space between the extraction cylindrical member and the cylindrical member Arranged on the outer circumference of the cylindrical member with the supply means And heating means that can heat the inside of the cylindrical member, and scraping means that is disposed in the upper space of the cylindrical member and can scrape off deposits attached to the inner wall surface of the cylindrical member. .

  A manufacturing apparatus for a fibrous carbon material according to claim 2 of the present invention simultaneously heats an upper space portion and a lower space portion of a cylindrical member in a heating range by a heating means in the manufacturing apparatus according to claim 1. It is set to get.

  Moreover, the manufacturing apparatus of the fibrous carbon material which concerns on Claim 3 of this invention, The rod-shaped body inserted so that raising / lowering in the cylindrical member from the upper end part in the opening / closing means in the manufacturing apparatus of Claim 1 was possible, The extraction opening provided at the lower end of the rod-like body is constituted by a valve body that can be opened and closed from above or below.

  Further, the fibrous carbon material producing apparatus according to claim 4 of the present invention uses a blade provided on the outer surface of the rod-like body of the opening / closing means as the scraping means in the producing apparatus according to claim 3. It is.

  According to a fifth aspect of the present invention, there is provided a manufacturing apparatus for fibrous carbon material, wherein the scraping means in the manufacturing apparatus according to the third aspect is fitted on the rod-shaped body of the opening / closing means and separately from the rod-shaped body. It is composed of a tubular body that can be moved up and down, and a blade body that is provided on the outer surface of the tubular body and can scrape off deposits on the inner wall surface of the tubular member.

  Furthermore, the manufacturing apparatus of the fibrous carbon material which concerns on Claim 6 of this invention, The rod-shaped body inserted in the cylindrical member from the upper end part so that the opening-and-closing means in the manufacturing apparatus of Claim 1 could be moved up and down, The take-off opening is provided at the lower end of the rod-like body and can be opened / closed from below, and the scraping means is fitted on the rod-like body of the opening / closing means and is lifted / lowered separately from the rod-like body. A tubular body provided in a possible manner and a blade body provided on the outer surface of the tubular body and capable of scraping off deposits on the inner wall surface of the tubular member.

  According to the above configuration, the granular material in which the catalyst is attached to the particles is supplied into the cylindrical member from above, fluidized by the reaction gas from below, and heated by the heating means arranged in the periphery to be fibrous. Since the carbon material is grown on the surface of the catalyst and discharged downward while being cooled by the inert gas supplied from the extraction cylinder member provided below, the entire apparatus is alternately heated and cooled. There is no need for this, so a fibrous carbon material can be continuously and efficiently grown, and a scraping means that can scrape off deposits adhering to the inner wall surface of the cylindrical member is provided. This makes it possible to easily remove deposits such as soot and tar adhering to the inner wall surface. That is, workability is improved and the production efficiency of the fibrous carbon material can be further improved.

It is sectional drawing which shows the structure of the manufacturing apparatus of the fibrous carbon material of the Example of this invention. It is a schematic cross section explaining the manufacturing method by the manufacturing apparatus. It is a schematic cross section explaining the manufacturing method by the manufacturing apparatus. It is sectional drawing which shows the structure of the modification of the manufacturing apparatus. It is sectional drawing which shows the structure of the modification of the manufacturing apparatus. It is sectional drawing which shows the structure of the other modification of the manufacturing apparatus.

Embodiments of a fibrous carbon material manufacturing apparatus according to the present invention will be described below with reference to the drawings.
The fibrous carbon material described here includes carbon nanocoils (CNC), carbon nanotubes (CNT), etc., but the dimensions may be larger than nano-order, but in this embodiment, The case of producing a carbon nanocoil will be described.

  That is, the manufacturing method using this manufacturing apparatus heats a granular material in which a catalyst such as iron, indium, and tin is supported on alumina particles as metal particles in a fluidized state using a reaction gas containing carbon. (That is, a thermal CVD method using a fluidized bed), a carbon nanocoil which is a product is obtained by growing carbon on the surface of alumina particles in a fibrous form.

First, the manufacturing apparatus of the fibrous carbon material which concerns on a present Example is demonstrated.
As shown in FIG. 1, the manufacturing apparatus includes a cylindrical member 1 that is arranged in the vertical direction and whose upper and lower ends are closed, and an upper portion for forming a fluidized bed that is arranged in an intermediate portion in the cylindrical member 1. A space A and a lower space B for introducing a reactive gas are partitioned, and a carbon nanocoil (hereinafter referred to as a product) extraction opening 2a is formed at the center and near the outer periphery of the extraction opening 2a. An inverted conical fluidized bed holding member 2 in which a plurality of gas introduction holes 2b are formed, an upper end opening disposed in the lower space B and connected to the extraction opening 2a, and a lower end opening The product take-out cylinder member 3 that can be connected to the product collection means 4, the opening / closing means 5 that can open and close the take-out opening 2 a, and the granular material in the upper space A of the tubular member 1. Granular material supply means 6 for supplying the above, cylindrical member 3 for extraction, and above For supplying a reactive gas containing carbon in the annular space C between the cylindrical member 1 (for example, an inert gas such as helium, argon, nitrogen, etc. mixed with acetylene gas as a gas containing carbon). Gas supply means 7, heating means 8 disposed on the outer periphery of the cylindrical member 1 and capable of heating the inside thereof, and attached to the inner wall surface disposed in the upper space A of the cylindrical member 1 It comprises scraping means 9 for scraping off the kimono.

  The tubular member 1 is composed of a cylindrical body 11 and an upper lid 12 and a lower lid 13 that close the upper and lower ends of the body 11, and the intermediate position in the interior is as described above. In this way, an inverted conical fluidized bed holding member (hereinafter simply referred to as a holding member) 2 having a circular extraction opening 2a formed at the center is disposed, and a horizontal partition is located above the interior thereof. 14 is provided, and the upper space A is further divided into an upper backflow prevention space (described later) D and a lower reaction space E for performing the thermal CVD method. The partition wall 14 is formed with an inverted conical guide port 14a for guiding the granular material supplied by the granular material supply means 6 to the reaction space E.

  The gas introduction holes 2b provided near the outer periphery of the take-out opening 2a of the holding member 2 are formed in a horizontal and radial direction, and at a plurality of locations (for example, 8 at regular intervals) on the same circumference. Are arranged radially (in a radial direction or in an oblique direction so as to form a swirling flow).

The upper lid 12 is provided with a first gas supply pipe (also referred to as a gas supply port) 21 in the vertical direction, and is provided with the granular material supply means 6 described above.
The granular material supply means 6 includes a granular material supply pipe 22 that is inserted through the upper lid 12 in the vertical direction, and a granular material connected to the upper end of the granular material supply pipe 22 via an opening / closing valve 23. And a container 24 for use. The first gas supply pipe 21 and the granular material supply pipe 22 are opened in the backflow prevention space D above the partition wall 14. In particular, the granular material supply pipe 22 has a lower end opening surface facing and approaching the guide port 14 a formed in the partition wall 14.

  The reactive gas supply means 7 provided in the lower lid part 13 is connected to a second gas supply pipe 25 provided with a tip opening inserted through the lower lid part 13 in the vertical direction, and the second gas supply pipe 25. And a reaction gas tank (not shown) for supplying the reaction gas. Further, a third gas supply pipe 26 capable of supplying an inert gas such as helium, argon, or nitrogen is connected to the extraction cylinder member 3 protruding outward from the lower lid portion 13. Further, a gas discharge pipe 27 for discharging the gas in the reaction space E is connected in a horizontal direction at a position immediately below the partition wall 14 of the body portion 11 of the cylindrical member 1.

  The opening / closing means 5 is provided with a rod-like body (also referred to as an operating rod) 31 that is inserted through the tubular member 1 through the upper lid portion 12, and a lower opening of the rod-like body 31, and an extraction opening 2 a is provided. It is comprised from the valve body 32 which can be closed from upper direction.

  The scraping means 9 is provided in the opening / closing means 5 for opening / closing the extraction opening 2a. That is, the plate-shaped scraper 33 is provided in the lower part of the rod-shaped body 31 and at a plurality of locations around it, for example, at three locations (every 120 degrees). The shape of the scraper 33 when viewed from the side is for scraping off deposits adhering to the inner wall surface of the body 11 of the cylindrical member 1 and the upper surface of the holding member 2. The inner wall surface of the body portion 11 and the upper surface of the holding member 2 are formed.

  Seal members 34 and 35 are provided in the insertion portion of the rod-shaped body 31 of the upper lid portion 12 and the insertion portion of the extraction cylinder member 3 of the lower lid portion 13, and the upper lid portion 12 and the lower lid portion 13 have Cooling water passages 36 and 37 for flowing cooling water are formed.

  In addition, a gap is provided in the insertion portion (hole) in the partition wall 14 of the rod-shaped body 31, but since this gap is small, gas leaks from the reaction space E to the backflow prevention space D. Is hardly generated and gas leakage is reliably prevented by the inert gas supplied to the backflow preventing space D (exemplification of the sealing function).

In addition, packings 38 and 39 are provided between the upper lid portion 12 and the trunk portion 11 and between the lower lid portion 13 and the trunk portion 11, and are configured so that these members can be disassembled from each other. Yes.
The recovery means 4 is composed of an on-off valve 41 provided on the take-out cylinder member 3 and a product recovery container 42 connected to the on-off valve 41, and the heating means 8 is an electric heating coil. 45 and a power source (not shown) connected to the electric heating coil 45, and the electric heating coil 45 extends between the reaction space E (also the upper space A) and the lower space B. It is arranged so that it can be heated. In other words, it is disposed across the gas preheating zone, the fluidized bed zone (below the reaction space E), and the exhaust zone (the upper side of the reaction space E) that are above the annular space C. In addition, the gas preheating zone which is the annular space C is a region in which the reaction gas supplied from the second gas supply pipe 25 is preheated to promote gas decomposition, and the fluidized bed zone has a uniform and stable temperature. The region where nanocoils are generated, and the exhaust zone is a region where the upper gas temperature is maintained and the temperature of the fluidized bed zone is made uniform.

  Further, the backflow prevention space D is supplied with inert gas from the first gas supply pipe 21 into the backflow prevention space D, so that carbides (by-products) such as soot and tar generated during thermal CVD. This prevents the catalyst function from being lost by adhering to the granular material supplied from the granular material supply pipe 22 into the space D for backflow prevention. In this sense, the backflow prevention space D can also be referred to as a catalyst deactivation prevention space.

Hereinafter, a method for producing carbon nanocoils will be described with reference to FIGS.
First, as shown in FIG. 2 (a), the granular material G in which the catalyst is supported on the particles is stored in the storage container 24 of the granular material supply means 6. The extraction opening 2 a is closed by a valve body 32.

  Next, electricity is supplied to the electric heating coil 45 of the heating means 8 to heat the temperature inside the cylindrical member 1 to a predetermined temperature. This temperature range is in the range of 300 to 900 ° C., and naturally, it depends on the product, that is, the product, and in the case of carbon nanocoils, it is heated to about 600 to 800 ° C. At this time, cooling water is supplied to the cooling water passages 36 and 37 to perform cooling, and the sealing materials 34 and 35 are protected.

Next, as shown in FIG. 2B, the on-off valve 23 is opened to supply the granular material G in the storage container 24 into the cylindrical member 1 through the granular material supply pipe 22.
At this time, while the reactive gas in which acetylene gas (gas containing carbon content) is contained in the inert gas from the second gas supply pipe 25 is supplied to the annular space C (also the lower space B), An inert gas is supplied from the first gas supply pipe 21 into the backflow prevention space D.

  In this state, when the granular material G is dropped into the reaction space E from the guide port 14a of the partition wall 14 and guided onto the holding member 2, the granular material G is fluidized and stirred by the reaction gas ejected from the introduction hole 2a. Is done.

  That is, the granular material G is fluidized and stirred in the reaction space E and heated by the heating means 8 so that carbon content adheres and grows on the surface of the catalyst of the granular material G by thermal decomposition of the reaction gas (thermal CVD method). ), Carbon nanocoils as products are formed.

  Then, as shown in FIG. 2C, after a predetermined time has elapsed, the valve body 32 is raised to open the extraction opening 2a, and the carbon nanocoil H as a product is removed from the extraction cylinder member 3 by the recovery means 4. It is discharged into a collection container 42.

  At this time, the inert gas is supplied from the second gas supply pipe 25 and the third gas supply pipe 26, and the reaction gas in the reaction space E is discharged and the product discharged from the extraction opening 2a is cooled. Is done.

  By the way, carbides such as soot and tar, which are by-products at the time of reaction, adhere to the cylindrical member 1 after the thermal CVD. However, depending on the product (product), the carbide itself inhibits product growth and is removed. Need arises. For this reason, as shown in FIG. 2 (d), in the state where the valve body 32 is lowered and the extraction opening 2a is closed, a gas containing air or oxygen is supplied from the second gas supply pipe 25, and the reaction space The carbide is removed by burning the carbide in the part E (also in the upper space part A). So-called baking cleaning is performed.

  In addition, at the time of this calcination cleaning and thermal CVD, an inert gas is supplied from the first gas supply pipe 21 to the backflow prevention space D (see FIGS. 2B and 2D), and the granular material supply portion. In this granular material supply portion, a heat insulation effect and a cooling effect can be obtained at the same time.

By repeating such an operation (work), carbon nanocoils can be continuously produced without lowering the temperature of the entire apparatus.
Further, when the operation is performed to some extent, as shown in FIG. 3, the clinker J or the like adheres to the inner wall surface of the cylindrical member 1. In this case, the scraper 33 is interposed via the rod-shaped body 31 of the scraping means 9. The clinker adhering to the inner wall surface may be scraped off by vertically moving and rotating.

  In this way, the granular material in which the catalyst is supported on the particles is supplied into the cylindrical member 1 from above, fluidized by the reaction gas from below, and heated by the heating means 8 arranged around the carbon nanoparticle. Since the coil is grown on the surface of the catalyst and discharged downward while being cooled by the inert gas supplied from the extraction cylinder member 3 provided below, the entire apparatus is alternately heated and cooled. Therefore, the carbon nanocoil can be produced continuously and efficiently, and the scraper 33 capable of scraping off the adhering matter adhering to the inner wall surface of the cylindrical member 1 is provided. Deposits such as soot and tar adhering to the inner wall surface can be easily removed. That is, workability is improved and the production efficiency of carbon nanocoils can be further improved.

  By the way, in the above embodiment, the valve body is provided so as to be positioned above the extraction opening. However, for example, as shown in FIG. 4, the valve body 32 'is positioned below the extraction opening 2a. Alternatively, it may be opened and closed from below.

  In this case, the scraper 33 is attached to the rod-like body 31 so that the scraper 33 is positioned upward when the extraction opening 2a is closed by the valve body 32 'so that the scraper 33 does not get in the way during thermal CVD. It is done. FIG. 5 shows the use state of the scraper 33. As can be seen from FIG. 5, when the scraper 33 is used, the deposited material scraped off with the valve body 32 ′ positioned below is dropped into the extraction cylinder member 3 as it is.

Furthermore, in the said Example, although the scraper 33 was attached to the outer periphery of the rod-shaped body 31, you may make it provide separately from the opening-closing means 5 as shown, for example in FIG.
The scraping means 9 'in this case will be described in detail. The cylindrical body 51 that is externally fitted to the rod-like body 31 with a gap (that is, loosely fitted) is inserted through the upper lid portion 12 in the vertical direction. In addition, a plurality of scrapers 52 similar to the above-described embodiment are provided around the lower portion of the cylindrical body 51.

  In this case, as a matter of course, the scraper 52 can be moved up and down regardless of the raising / lowering operation of the valve body 32, so that the deposits can be scraped off freely. Therefore, it is possible to improve the efficiency of scraping off the adhered matter.

A Upper space part B Lower space part C Annular space part D Backflow prevention space part E Reaction space part 1 Cylindrical member 2 Fluidized bed holding member 2a Extraction opening 2b Gas introduction hole 3 Extraction cylinder member 4 Recovery means 5 Opening / closing Means 5 'Opening / closing means 6 Granular body supply means 7 Reactive gas supply means 8 Heating means 9 Scraping means 9' Scraping means 11 Body 12 Upper lid part 13 Lower lid part 14 Partition 14a Guide port 21 First gas supply pipe 22 Granularity Body supply pipe 24 Storage container 25 Second gas supply pipe 26 Third gas supply pipe 27 Gas discharge pipe 31 Rod-like body 32 Valve body 32 'Valve body 33 Scraper 42 Recovery container 45 Electric heating coil 51 Tubular body 52 Scraper

Claims (6)

An apparatus for producing a fibrous carbon material by growing a fibrous carbon in a granular body by fluidizing and heating the granular body having a catalyst supported on the particles using a reaction gas containing carbon,
A cylindrical member that is arranged in the vertical direction and whose upper and lower ends are closed, and is divided into an upper space part for forming a fluidized bed and a lower space part for supplying a reactive gas, which are arranged in an intermediate part in the cylindrical member. And an inverted conical fluidized bed holding member in which an opening for extraction of the fibrous carbon material is formed in the center and a plurality of gas introduction holes are formed near the outer periphery of the extraction opening, and in the lower space portion A tubular member for taking out carbon fiber material, the upper end opening of which is connected to the extraction opening and the lower end opening of which can be connected to the collecting means, and the extraction opening can be opened and closed freely. Reactive opening / closing means, granular material supply means for supplying granular material to the upper space of the cylindrical member, and reactive gas for supplying reactive gas into the annular space between the extraction cylindrical member and the cylindrical member Arranged on the outer circumference of the cylindrical member with the supply means And heating means capable of heating the inside of the cylindrical member, and scraping means disposed in the upper space of the cylindrical member and capable of scraping off deposits adhering to the inner wall surface of the cylindrical member. An apparatus for producing a fibrous carbon material.   An apparatus for producing a fibrous carbon material, wherein the heating range by the heating means is set so that the upper space portion and the lower space portion of the cylindrical member can be heated simultaneously.   The opening / closing means is composed of a rod-like body inserted in the cylindrical member from the upper end portion so as to be movable up and down, and a valve body provided at the lower end of the rod-like body, which can be opened and closed from above or below. The manufacturing apparatus of the fibrous carbon material of Claim 1 characterized by these.   The apparatus for producing a fibrous carbon material according to claim 3, wherein a blade provided on the outer surface of the rod-like body of the opening / closing means is used as the scraping means.   A tubular body that is externally fitted to the rod-shaped body of the opening / closing means and that can be lifted and lowered separately from the rod-shaped body, and an attachment to the inner wall surface of the tubular member that is disposed on the outer surface of the tubular body The apparatus for producing a fibrous carbon material according to claim 3, wherein the apparatus comprises a blade body that can scrape off.   The opening / closing means is composed of a rod-like body inserted into the cylindrical member from the upper end portion so as to be movable up and down, and a take-off opening provided at the lower end of the rod-like body, which can be opened and closed from below, and scraped. The dropping means is externally fitted to the rod-like body of the opening / closing means and can be moved up and down separately from the rod-like body, and the attached matter on the inner wall surface of the tubular member provided on the outer surface of the tubular body The apparatus for producing a fibrous carbon material according to claim 1, wherein the apparatus comprises a blade body that can scrape off.

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